CN111569914A - Bimetal phosphide composite material and preparation method and application thereof - Google Patents
Bimetal phosphide composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 239000004094 surface-active agent Substances 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229920001400 block copolymer Polymers 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000001338 self-assembly Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000002073 nanorod Substances 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229920000359 diblock copolymer Polymers 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 229920006030 multiblock copolymer Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 29
- 230000003197 catalytic effect Effects 0.000 abstract description 26
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000011943 nanocatalyst Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000877 morphologic effect Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/33—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to the technical field of nano materials and catalysts, and discloses a bimetal phosphide composite material and a preparation method and application thereof. The chemical formula of the composite material is FeP/RaP, wherein R is nickel element or cobalt element, a is 1 or 2; meanwhile, the preparation method is simple to operate and convenient for industrial production, and the bimetallic phosphide composite material prepared by the method has a nano rod-like structure, so that the structural stability and catalytic activity of the material can be improved. Meanwhile, the bimetallic phosphide composite material provided by the invention is used in electrocatalytic oxygen evolution reaction, and has better catalytic activity and faster catalytic kinetics performance.
Description
Technical Field
The invention relates to the technical field of nano materials and catalysts, in particular to a bimetal phosphide composite material and a preparation method and application thereof.
Background
Transition metal phosphide attracts extensive attention of researchers due to its characteristics of good hydrogen evolution or oxygen evolution catalytic performance, good electrochemical performance, stability, low cost and the like. Iron, cobalt and nickel are used as the first row of transition metal elements, natural resources are rich, and oxides, sulfides and phosphides of the elements have excellent hydrogen evolution and oxygen evolution catalytic properties. Materials such as iron phosphide, nickel phosphide and cobalt phosphide show better catalytic performance in the electrolytic water reaction due to unique electronic structure, excellent physical performance and good catalytic activity. Accordingly, various bimetallic phosphide composites of different compositions and different morphologies were synthesized and used as electrolytic water reaction catalysts.
Disclosure of Invention
The invention aims to solve the problems of high preparation cost and low catalytic activity of an oxygen evolution catalyst in the prior art, and provides a bimetallic phosphide composite material, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides a bimetal phosphide composite material, wherein the chemical formula of the composite material is FeP/RaP, wherein R is nickel element or cobalt element, and a is 1 or 2.
Preferably, the bimetallic phosphide composite material has a nanorod structure.
The second aspect of the present invention provides a method for preparing a bimetal phosphide composite material, which comprises the following steps:
(1) mixing a first metal compound, a second metal compound, a surfactant, an acid and an organic alcohol to obtain a mixed solution;
(2) performing solvent volatilization self-assembly and roasting on the mixed solution to obtain a bimetal precursor;
(3) carrying out phosphating treatment on the bimetal precursor to obtain a bimetal phosphide composite material;
wherein the first metal is iron and the second metal is nickel or cobalt.
Preferably, the surfactant is a block copolymer.
Preferably, the mixing in step (1) comprises: (a) carrying out first mixing on a first metal compound, partial surfactant, partial acid and partial organic alcohol to obtain a solution A; (b) carrying out second mixing on the second metal compound, the residual part of the surfactant, the residual part of the acid and the residual part of the organic alcohol to obtain a solution B; (c) and carrying out third mixing on the solution A and the solution B to obtain the mixed solution.
Preferably, the conditions under which the solvent volatilizes to self-assemble comprise: the temperature is 30-200 ℃, preferably 100-160 ℃; the time is 1-10h, preferably 2-6 h.
In a third aspect, the present invention provides a bimetallic phosphide composite material prepared by the above method.
The fourth aspect of the invention provides an application of the bimetal phosphide composite material in electrocatalytic oxygen evolution reaction.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method mainly adopts a solvent volatilization self-assembly preparation method, and the preparation process is simple and easy to operate and is convenient for industrial production;
(2) the invention adopts transition metal as raw material, reduces the catalytic cost, and simultaneously, the bimetal has synergistic effect, so that the bimetal phosphide composite material has better catalytic activity and faster catalytic dynamic performance;
(3) the bimetallic phosphide composite material provided by the invention is of a nano-rod-shaped structure, has a larger specific surface area, and is more beneficial to improving the catalytic activity of the material.
Drawings
FIG. 1 shows FeP/Ni prepared in example 12X-ray diffraction pattern (XRD pattern) of the P material S1;
FIG. 2 shows FeP/Ni prepared in example 12Scanning electron micrographs (SEM images) of P material S1;
FIG. 3 is an X-ray diffraction pattern (XRD pattern) of the FeP/CoP material S2 obtained in example 2;
FIG. 4 is a Scanning Electron Micrograph (SEM) of the FeP/CoP material S2 obtained in example 2.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a bimetal phosphide composite material in a first aspect, wherein the chemical formula of the composite material is FeP/RaP, wherein R is nickel element or cobalt element, and a is 1 or 2.
According to the present invention, preferably, the bimetal phosphide composite material has a nanorod structure. The composite material provided by the invention has a stable morphology structure.
According to a preferred embodiment of the present invention, when the bimetal is iron and nickel, the bimetal phosphide composite material is FeP/Ni2P material, and the FeP/Ni2The P material has a nanorod structure.
According to a preferred embodiment of the present invention, when the bimetal is iron and cobalt, the bimetal phosphide composite material is a FeP/CoP material, and the FeP/CoP material has a nanorod structure.
In the invention, because of the synergistic effect between the double metals, the double metal phosphide composite material has better catalytic activity and faster catalytic kinetic performance.
The second aspect of the present invention provides a method for preparing a bimetal phosphide composite material, which comprises the following steps:
(1) mixing a first metal compound, a second metal compound, a surfactant, an acid and an organic alcohol to obtain a mixed solution;
(2) performing solvent volatilization self-assembly and roasting on the mixed solution to obtain a bimetal precursor;
(3) carrying out phosphating treatment on the bimetal precursor to obtain a bimetal phosphide composite material;
wherein the first metal is iron and the second metal is nickel or cobalt.
The invention adopts transition metals (iron and nickel, iron and cobalt) as active components, so that the catalytic cost is reduced on one hand, and the bimetal has synergistic effect on the other hand, thereby being more beneficial to improving the catalytic activity.
In the present invention, there is a wide selection range of the first metal compound and the second metal compound, preferably, the first metal compound and the second metal compound are each independently a soluble metal compound, further preferably, the first metal compound is at least one selected from the group consisting of iron chloride, iron sulfate, and iron nitrate, the second metal compound is at least one selected from the group consisting of nickel chloride, nickel sulfate, and nickel nitrate, or the second metal compound is at least one selected from the group consisting of cobalt chloride, cobalt sulfate, and cobalt nitrate.
According to the present invention, in order for the dual metal phosphide composite material to have a uniform morphological structure and a porous structure, it is preferred that the surfactant is a block copolymer.
In the present invention, there is a wide selection range of the block copolymer, and preferably, the block copolymer is selected from diblock copolymers, triblock copolymersAt least one of a block copolymer and a multi-block copolymer, preferably a triblock copolymer, more preferably a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, more preferably P123, wherein the molecular formula of P123 is PEO20PPO70PEO20And the molecular weight is 5800. The surfactant described in the examples is exemplified by P123, but the invention is not limited thereto.
The block copolymer of the present invention may be obtained commercially or may be prepared, and the present invention is not particularly limited thereto.
According to the present invention, preferably, the acid is an inorganic acid, further preferably at least one selected from the group consisting of nitric acid, sulfuric acid and hydrochloric acid, and more preferably nitric acid, such as concentrated nitric acid and/or dilute nitric acid.
Preferably, the organic alcohol is an organic alcohol having a carbon number of 1-5, more preferably at least one selected from the group consisting of methanol, ethanol, propanol, isopropanol and butanol, and still more preferably n-butanol.
According to the present invention, preferably, the molar ratio of the first metal compound, the second metal compound and the surfactant is 1: 0.1-1.5: 0.01 to 0.1, more preferably 1: 0.8-1.2: 0.02 to 0.06, more preferably 1: 1: 0.02-0.06.
Preferably, the molar ratio of the first metal compound to the organic alcohol is 1: 5 to 50, more preferably 1: 15-30. The preferred embodiment is more favorable for obtaining the composite material with a uniform morphological structure.
Preferably, the volume ratio of the acid to the organic alcohol is 1: 1 to 15, more preferably 1: 5-10. The use of this preferred embodiment is more advantageous for the stabilization of micelles in solution.
In the present invention, the mixing manner in the step (1) is not particularly limited as long as the first metal compound, the second metal compound, the surfactant, the acid and the organic alcohol are uniformly mixed, wherein the mixing is selected from one-step mixing and/or step-by-step mixing, and the one-step mixing refers to directly mixing the first metal compound, the second metal compound, the surfactant, the acid and the organic alcohol according to a certain ratio; the step mixing is to mix the first metal compound with part of the surfactant, part of the acid and part of the organic alcohol, mix the second metal compound with the rest of the surfactant, the rest of the acid and the rest of the organic alcohol, and mix the mixed solution containing the first metal compound with the mixed solution containing the second metal compound.
In order to further improve the structural stability and catalytic activity of the dual metal phosphide composite material, preferably, the mixing in step (1) comprises:
(a) carrying out first mixing on a first metal compound, partial surfactant, partial acid and partial organic alcohol to obtain a solution A;
(b) carrying out second mixing on the second metal compound, the residual part of the surfactant, the residual part of the acid and the residual part of the organic alcohol to obtain a solution B;
(c) and carrying out third mixing on the solution A and the solution B to obtain the mixed solution.
According to the present invention, preferably, the conditions of the first mixing, the second mixing and the third mixing each independently include: the temperature is 20-60 ℃, preferably 30-50 ℃; the time is 10-60min, preferably 20-40 min.
In the present invention, the first mixing method is not particularly limited as long as the first metal compound is uniformly mixed with part of the surfactant, part of the acid, and part of the organic alcohol. Preferably, part of the surfactant, part of the acid and part of the organic alcohol are mixed first, and then the first metal compound is added. The preferred first mixing mode is favorable for obtaining the composite material with a uniform morphological structure.
According to a preferred embodiment of the invention, part of the surfactant, part of the acid and part of the organic alcohol are mixed and dissolved in a thermostatic water bath at the temperature of 20-60 ℃, and then the soluble iron compound is added and stirred for 10-60min to obtain a solution A.
In the present invention, the second mixing method is not particularly limited as long as the second metal compound is uniformly mixed with the remaining part of the surfactant, the remaining part of the acid, and the remaining part of the organic alcohol. Preferably, the remaining part of the surfactant, the remaining part of the acid and the remaining part of the organic alcohol are mixed first, and then the second metal compound is added. The preferred second mixing approach is advantageous for composite materials with uniform morphology.
According to a preferred embodiment of the invention, the remaining part of the surfactant, the remaining part of the acid and the remaining part of the organic alcohol are mixed and dissolved in a thermostatic water bath at 20-60 ℃, and then the soluble nickel compound or the soluble cobalt compound is added and stirred for 10-60min to obtain a solution B.
In the present invention, the third mixing method is not particularly limited as long as the solution a and the solution B are uniformly mixed. Preferably, the solution A and the solution B are stirred for 10-60min at the temperature of 20-60 ℃ to obtain a mixed solution.
In a preferred embodiment of the invention, the surfactant, the acid and the organic alcohol are added in two portions, respectively, in steps (a) and (b), with a wide range of ratios of the two portions. Preferably, the molar ratio of the partial surfactant of step (a) to the remaining surfactant of step (b) is 1: 0.1 to 5; the volume ratio of the partial acid of the step (a) to the residual acid of the step (b) is 1: 0.1 to 5; the volume ratio of the part of organic alcohol in the step (a) to the rest of organic alcohol in the step (b) is 1: 0.1-5, but the present invention is not limited thereto.
According to the present invention, preferably, the conditions under which the solvent volatilizes for self-assembly include: the temperature is 30-200 ℃, preferably 100-160 ℃; the time is 1-10h, preferably 2-6 h. The preferred conditions are adopted, so that the nano-structure material with uniform morphology can be obtained quickly. In the examples of the present invention, the solvent evaporation is carried out in an oven by self-assembly, but the present invention is not limited thereto.
According to a preferred embodiment of the present invention, the step (2) further comprises: and sequentially cooling, washing, separating and drying the product of the solvent volatilization self-assembly, and then roasting.
In the present invention, the cooling, washing and separation are not particularly limited, and are all conventional technical means in the art. In the embodiment of the present invention, the solvent is volatilized from the self-assembled product, and after naturally cooling to room temperature, the self-assembled product is washed with ethanol 3 to 5 times, and then centrifuged, but the present invention is not limited thereto.
In the present invention, the drying environment is not particularly limited. Preferably, the drying is performed under air conditions, vacuum conditions, freezing conditions, and further preferably under vacuum conditions.
In the present invention, there is a wide range of selection of the drying conditions, and preferably, the drying conditions include: the temperature is 20-80 ℃, preferably 30-60 ℃; the time is 10-24h, preferably 12-20 h.
Preferably, the conditions of the calcination include: the temperature is 100-450 ℃, and preferably 100-300 ℃; the time is 5-20h, preferably 8-15 h.
According to a preferred embodiment of the present invention, the dried product is calcined in a muffle furnace at a temperature of 2-10 ℃/min to 450 ℃ for 5-20 h.
In the present invention, the operation mode of the phosphating is not particularly limited, and the phosphating preferably includes: contacting the bimetallic precursor with a phosphorus source.
In the present invention, in order to fully perform the phosphorization of the metal precursor and obtain a purer phosphide material, preferably, the phosphorization treatment is performed under the condition of isolating air, further preferably, the phosphorization treatment is performed in an inert atmosphere or vacuum, preferably in an inert atmosphere, and the inert atmosphere is provided by inert gas; the inert gas is selected from at least one of nitrogen, helium and argon, preferably nitrogen.
Preferably, the conditions of the phosphating treatment include: the temperature is 150-450 ℃, preferably 200-400 ℃, and the time is 1-10h, preferably 2-5 h.
In the present invention, there is a wide selection of the phosphorus source, preferably selected from inorganic phosphorus and/or organic phosphorus, preferably inorganic phosphorus; further preferably, the inorganic phosphorus is selected from red phosphorus and/or sodium hypophosphite, preferably sodium hypophosphite.
Preferably, the mass ratio of the bimetal precursor to the phosphorus source is 1: 10-50, more preferably 1: 10-30. The optimized mass ratio is more favorable for fully phosphorizing the bimetal precursor.
According to a preferred embodiment of the present invention, the bimetal precursor is placed in a porcelain boat, placed in a tube furnace, and the porcelain boat containing a phosphorus source is added at the air inlet end, and the temperature is raised to 150-450 ℃ at a constant temperature raising rate (1-10 ℃/min) in the tube furnace continuously filled with nitrogen for reaction for 1-10 h.
In a third aspect, the present invention provides a bimetallic phosphide composite material prepared by the above method.
The invention provides an application of the bimetal phosphide composite material in electrocatalytic oxygen evolution reaction.
In the invention, the bimetal phosphide composite material is used in the electrocatalytic oxygen evolution reaction, and due to the synergistic effect of the bimetal, the bimetal phosphide treatment material has good catalytic activity and faster catalytic kinetics performance.
The present invention will be described in detail below by way of examples.
P123(PEO20PPO70PEO20Molecular weight 5800) was purchased from Sigma Aldrich (Sigma-Aldrich).
Example 1
(1) 1.16g P123, 1.32mL concentrated nitric acid, 11mL n-butanol, and 0.01mol iron nitrate (Fe (NO)3)3·9H2O) is completely dissolved in a constant temperature water bath at 40 ℃, and is stirred for 10min to obtain a solution A; 1.45g P123, 1.53mL concentrated nitric acid, 13mL n-butanol and 0.01mol nickel nitrate (Ni (NO)3)2·6H2O) is completely dissolved in a constant temperature water bath at 40 ℃, and is stirred for 10min to obtain a solution B; mixing the solution A and the solution B in a constant-temperature water bath at 40 ℃ and stirring for 30min to obtain a mixed solution;
(2) transferring the mixed solution into a 120 ℃ drying oven, heating for 3.5h, cooling to room temperature, washing with ethanol for 3 times, centrifugally separating, drying in a 40 ℃ vacuum drying oven for 12h, and roasting the dried product in a muffle furnace at a temperature rise rate of 5 ℃/min to 150 ℃ for 12h to obtain an iron/nickel precursor;
(3) 20mg of the Fe/Ni precursor was placed in a porcelain boat and in a tube furnace, and N was continuously introduced2Adding a porcelain boat containing 400mg of sodium hypophosphite at the air inlet end, setting a tube furnace program, heating to 300 ℃ at a heating rate of 2 ℃/min, roasting at the temperature for 3h, and cooling to obtain FeP/Ni2P material S1.
Wherein the FeP/Ni2The XRD pattern of the P material S1 is shown in figure 1, wherein diffraction peaks of 2 theta at 32.7 degrees, 37.12 degrees, 46.9 degrees, 48.3 degrees, 56.1 degrees and 59.6 degrees are respectively assigned to (011), (111), (202), (211), (212) and (020) crystal planes (JCPDS No.78-1443) of FeP; diffraction peaks of 2 theta at 40.8 DEG, 44.6 DEG, 47.3 DEG and 54.2 DEG, respectively ascribed to Ni2The (111), (201), (210) and (300) crystal planes of P (JCPDS No. 03-0953).
The FeP/Ni2The SEM of P material S1 is shown in FIG. 2, which shows the FeP/Ni2The P material S1 has a nanorod structure.
Example 2
(1) 1.16g P123, 1.32mL concentrated nitric acid, 11mL n-butanol, and 0.01mol iron nitrate (Fe (NO)3)3·9H2O) is completely dissolved in a constant temperature water bath at 40 ℃, and is stirred for 10min to obtain a solution A; 1.45g P123, 1.53mL concentrated nitric acid, 13mL n-butanol and 0.01mol cobalt nitrate (Co (NO)3)2·6H2O) is completely dissolved in a constant temperature water bath at 40 ℃, and is stirred for 10min to obtain a solution B; mixing the solution A and the solution B in a constant-temperature water bath at 40 ℃ and stirring for 30min to obtain a mixed solution;
(2) transferring the mixed solution into a 120 ℃ drying oven, heating for 3.5h, cooling to room temperature, washing with ethanol for 3 times, centrifugally separating, drying in a 40 ℃ vacuum drying oven for 12h, and roasting the dried product in a muffle furnace at a temperature rise rate of 5 ℃/min to 150 ℃ for 12h to obtain an iron/cobalt precursor;
(3) 20mg of Fe/Co precursor was placed in a porcelain boat, placed in a tube furnace, and N was continuously introduced2Adding a porcelain boat containing 400mg of sodium hypophosphite at the air inlet end, setting a tube furnace program, heating to 300 ℃ at the heating rate of 2 ℃/min, reacting for 2h, and cooling to obtain the FeP/CoP material S2.
Wherein, the XRD pattern of the FeP/CoP material S2 is shown in figure 3, wherein, the diffraction peaks of 2 theta at 32.7 degrees, 37.12 degrees, 46.9 degrees, 48.3 degrees, 56.1 degrees and 59.6 degrees are respectively assigned to the (011), (111), (202), (211), (212) and (020) crystal planes (JCPDS No.78-1443) of FeP; diffraction peaks of 2 θ at 31.6 °, 36.3 °, 48.1 ° and 56.8 ° are assigned to the (011), (111), (211) and (301) crystal planes of CoP, respectively (JCPDS No. 29-0497).
An SEM picture of the FeP/CoP material S2 is shown in FIG. 4, which shows that the FeP/CoP material S2 has a nanorod structure.
Comparative example 1
The procedure is as in example 1, except that 0.01mol of nickel nitrate (Ni (NO) is not added3)2·6H2O) to obtain the FeP material D1.
Comparative example 2
The procedure is as in example 1, except that 0.01mol of iron nitrate (Fe (NO) is not added3)3·9H2O) to obtain Ni2P-material D2.
Comparative example 3
The procedure is as in example 2, except that 0.01mol of iron nitrate (Fe (NO) is not added3)3·9H2O), yielding CoP material D3.
Test example
The bimetallic phosphide composite materials prepared in examples 1-2 and comparative examples 1-3 were subjected to the preparation of an electrocatalyst working electrode, which comprises:
(1) preparing a working electrode solution: respectively adding 4mg of the bimetallic phosphide composite materials S1-S2 and D1-D3 into a mixed solution containing Nafion solution (16 muL, 5 wt%), isopropanol (264 muL) and deionized water (520 muL), and carrying out ultrasonic treatment for 10-20min to obtain a working electrode solution;
(2) preparation of a working electrode: dripping the working electrode solution (12 mu L) onto a newly polished rotary disc glassy carbon electrode, and airing to obtain oxygen evolution catalysts P1-P2 and Q1-Q3;
(3) construction of a three-electrode system: and (3) constructing a three-electrode system by taking the oxygen evolution catalyst as a working electrode, taking a 1mol/L KOH solution as an electrolyte, taking a carbon rod as a counter electrode and taking Hg/HgO electrodes as reference electrodes respectively.
The electrochemical workstation of a three-electrode system CHI760E is adopted, the electrolyte is KOH solution (1mol/L), the three-electrode system using the bimetallic phosphide composite material is subjected to an electrocatalyst performance test, and the test result is shown in Table 1, wherein the overpotential is that the current density reaches 10mA/cm2The required overpotential.
TABLE 1
The results of table 1 show that when the bimetallic phosphide composite material provided by the invention is used in an oxygen evolution catalyst, the bimetallic phosphide composite material has a lower overpotential and a smaller tafel slope, that is, the bimetallic phosphide composite material provided by the invention has higher catalytic activity and faster catalytic kinetics performance.
By comparing the oxygen evolution performance test results of the oxygen evolution catalysts P1, Q1 and Q2 in 1mol/L KOH, it can be known that:
(1) when the current density reaches 10mA/cm2Then, the bimetal phosphide FeP/Ni2P requires an overpotential of 300mV compared to the monometallic phosphides FeP (380mV) and Ni2When two materials of P (390mV) are respectively used as catalysts, the overpotential required for achieving the current density is small, and the results show that the bimetallic phosphide (FeP/Ni)2P) has higher oxygen evolution catalytic performance when used as a catalyst;
(2) bimetallic phosphide FeP/Ni2The Tafel slope value of P is 48mV/dec, compared with monometallic phosphide FeP (73mV/dec) and Ni2The Tafel slope values of P (84mV/dec) were all small, and the above results indicate that the bimetallic phosphide (FeP/Ni)2P) as a catalyst has a higher rate of activityCatalytic kinetics performance of (2).
By comparing the oxygen evolution performance test results of the oxygen evolution catalysts P2, Q1 and Q3 in 1mol/L KOH, it can be known that:
(1) when the current density reaches 10mA/cm2When the bimetallic phosphide FeP/CoP is used as a catalyst, the overpotential required by the bimetallic phosphide FeP/CoP is 350mV, which is smaller than that required by two materials, namely the monometallic phosphide FeP (380mV) and the CoP (409mV), when the two materials are respectively used as the catalyst, the overpotential required by reaching the current density is both small, and the result shows that the bimetallic phosphide (FeP/CoP) has higher oxygen evolution catalytic performance when being used as the catalyst.
(2) The Tafel slope values for the bimetallic phosphide FeP/CoP were 66mV/dec, which are lower than those for both the monometallic phosphide FeP (73mV/dec) and CoP (77mV/dec), indicating faster catalytic kinetics for the bimetallic phosphide (FeP/CoP) as a catalyst.
From the above results, it can be concluded that the bimetallic phosphide material has better catalytic activity and faster catalytic kinetics performance as an oxygen evolution catalyst due to the synergistic effect between the metallic iron and the nickel or the metallic iron and the cobalt in the bimetallic composite material.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A bimetal phosphide composite material, wherein the chemical formula of the composite material is FeP/RaP, wherein R is nickel element or cobalt element, a is 1 or 2;
preferably, the bimetallic phosphide composite material has a nanorod structure.
2. A method for preparing a bimetallic phosphide composite material, which comprises the following steps:
(1) mixing a first metal compound, a second metal compound, a surfactant, an acid and an organic alcohol to obtain a mixed solution;
(2) performing solvent volatilization self-assembly and roasting on the mixed solution to obtain a bimetal precursor;
(3) carrying out phosphating treatment on the bimetal precursor to obtain a bimetal phosphide composite material;
wherein the first metal is iron and the second metal is nickel or cobalt.
3. The method of claim 2, wherein the first metal compound and the second metal compound are each independently a soluble metal compound;
preferably, the first metal compound is selected from at least one of ferric chloride, ferric sulfate and ferric nitrate;
preferably, the second metal compound is selected from at least one of nickel chloride, nickel sulfate and nickel nitrate, or,
preferably, the second metal compound is selected from at least one of cobalt chloride, cobalt sulfate and cobalt nitrate;
preferably, the surfactant is a block copolymer;
preferably, the block copolymer is selected from at least one of a diblock copolymer, a triblock copolymer and a multiblock copolymer, preferably a triblock copolymer;
preferably, the triblock copolymer is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, more preferably P123;
preferably, the acid is selected from at least one of nitric acid, sulfuric acid, and hydrochloric acid;
preferably, the organic alcohol is an organic alcohol of C1-C5, and further preferably at least one selected from methanol, ethanol, propanol, isopropanol, and butanol.
4. The method according to claim 2 or 3, wherein the molar ratio of the first metal compound, the second metal compound and the surfactant is 1: 0.1-1.5: 0.01 to 0.1, preferably 1: 0.8-1.2: 0.02-0.06;
preferably, the molar ratio of the first metal compound to the organic alcohol is 1: 5 to 50, more preferably 1: 15-30 parts of;
preferably, the volume ratio of the acid to the organic alcohol is 1: 1 to 15, more preferably 1: 5-10.
5. The method of any one of claims 2-4, wherein the mixing in step (1) comprises:
(a) carrying out first mixing on a first metal compound, partial surfactant, partial acid and partial organic alcohol to obtain a solution A;
(b) carrying out second mixing on the second metal compound, the residual part of the surfactant, the residual part of the acid and the residual part of the organic alcohol to obtain a solution B;
(c) carrying out third mixing on the solution A and the solution B to obtain a mixed solution;
preferably, the conditions of the first mixing, the second mixing and the third mixing each independently comprise: the temperature is 20-60 ℃, preferably 30-50 ℃; the time is 10-60min, preferably 20-40 min.
6. The method of claim 2, wherein the conditions under which the solvent volatilizes self-assembly comprise: the temperature is 30-200 ℃, preferably 100-160 ℃; the time is 1 to 10 hours, preferably 2 to 6 hours;
preferably, step (2) further comprises: sequentially cooling, washing, separating and drying the product of the solvent volatilization self-assembly, and then roasting;
preferably, the drying is carried out under air conditions, vacuum conditions or freezing conditions, preferably under vacuum conditions;
preferably, the drying conditions include: the temperature is 20-80 ℃, preferably 30-60 ℃; the time is 10 to 24 hours, preferably 12 to 20 hours;
preferably, the conditions of the calcination include: the temperature is 100-450 ℃, and preferably 100-300 ℃; the time is 5-20h, preferably 8-15 h.
7. The method of claim 2, wherein the phosphating process comprises: contacting the bimetallic precursor with a source of phosphorus;
preferably, the phosphating treatment is carried out in an inert atmosphere or vacuum, preferably in an inert atmosphere, the inert atmosphere being provided by an inert gas;
preferably, the inert gas is selected from at least one of nitrogen, helium and argon, preferably nitrogen;
preferably, the conditions of the phosphating treatment include: the temperature is 150-450 ℃, preferably 200-400 ℃, and the time is 1-10h, preferably 2-5 h.
8. A process according to claim 7, wherein the phosphorus source is selected from inorganic phosphorus and/or organic phosphorus, preferably inorganic phosphorus;
preferably, the inorganic phosphorus is selected from red phosphorus and/or sodium hypophosphite, preferably sodium hypophosphite;
preferably, the mass ratio of the bimetal precursor to the phosphorus source is 1: 10-50, preferably 1: 10-30.
9. A bimetallic phosphide composite material prepared by the method of any one of claims 2 to 8.
10. Use of the bimetallic phosphide composite material as claimed in claim 1 or 9 in electrocatalytic oxygen evolution reactions.
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